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研究生： 郭窈伶
Kuo, Yao-Ling
論文名稱： 錫鋅共晶銲錫與電鍍鎳層之界面反應研究
Investigation of the Interfacial Reaction between Eutectic Sn-9Zn Lead-free Solder Alloy and Electroplated Ni
指導教授： 林光隆
Lin, Kuang-Lung
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 72
中文關鍵詞： 界面反應 、錫鋅共晶銲錫 、電鍍鎳
外文關鍵詞： interfacial reaction, Sn-9Zn, electroplated Ni
相關次數： 點閱：62  下載：2 
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    • 在電子構裝中，銲錫合金是用以接合電子元件與基板，因此銲錫接點的接合強度是非常重要的性質。由於做為銲錫隆點底層金屬（Under Bump Metallurgy；UBM）的銅會與銲錫快速的反應形成過多介金屬化合物，造成接點失效。近來在銲錫與銅銲墊之間鍍上一層鎳，利用鎳與銲錫反應速率較低的特性，做為擴散阻礙層，避免銅銲墊被快速地消耗。
    而共晶錫鋅銲錫因具有較低的熔點、良好的機械性質以及低廉的成本，成為取代傳統共晶錫鉛銲錫的一個很好的選擇。本研究係觀察電鍍鎳與液態錫鋅銲錫間之界面反應，改變反應溫度與時間，量測其生成物厚度的變化，以探討其間所生成反應層之成長機制以及其成長所需的活化能。研究結果顯示，在230 ~ 290℃生成反應層總厚度會隨著反應時間的增加而增厚，且隨溫度提高，反應層之成長由界面反應與擴散行為混合控制轉為由擴散行為控制，其成長所需活化能為71.3 kJ/mol。
    以聚焦離子束顯微鏡觀察經過表面微蝕刻後的反應界面，可清楚看到所生成的反應層不只一層。經EDS分析各層成份，發現在250℃生成之反應層包括Ni5Zn21及鎳鋅固溶層，將反應溫度提高至270℃之反應層為Ni5Zn21、鎳鋅固溶層及NiZn3，而在290℃之反應層為Ni5Zn21與NiZn3。在不同反應溫度反應10 ~ 120分鐘，各反應層中僅Ni5Zn21隨反應時間有明顯增厚的現象，NiZn3及鎳鋅固溶層隨反應時間厚度沒有明顯變化。

    Soldering has been the key assembly and interconnection technology for electronic products. Solder joints have long been recognized as the weak links in electronic products, and the reliability of each individual joint can control the overall lifespan of an electronic product. Copper is one of the most popular choices for the surface layer of the under bump metallurgy (UBM), mainly due to its good wetting property with solders. During assembly or normal service of the device, the Cu layer will be consumed completely, causing failure in solder joints. Therefore, Ni is used as a diffusion barrier layer to prevent the rapid interfacial reaction between the solder and Cu layer.
    Eutectic Sn-9Zn solder has been considered as one of the alternatives for conventional eutectic Sn-37Pb due to the low melting point, excellent mechanical properties and low cost. The present work investigated the interfacial reaction between electroplated Ni and molten eutectic Sn-9Zn solder. The experiment was conducted under the temperature range between 230 and 290℃ for 10 to 120 min. During the reaction, the intermetallic compound (IMC) formed between Ni layer and the solder. The kinetics of IMC growth was investigated by measuring the thickness of IMC after solid-liquid reaction at different temperatures for different period of time. The results show that the thickness of the total IMC layer increased with increasing reaction time. The controlling mechanism of the growth of the IMC layer changes from mixed controlled to diffusion controlled. The activation energy of the growth was estimated to be 71.3 kJ/mol.
    The interaction gives rise to more than one IMC at the interface as revealed by FIB (Focus Ion Beam) treatment. According to the EDS results, the IMC formed at 250℃ were Ni5Zn21 and Ni-Zn solid solution layer. At 270℃, NiZn3 formed between Ni5Zn21 and Ni-Zn solid solution. As the temperature increases up to 290℃, Ni5Zn21 and NiZn3 were found at the interface. Under different temperatures, the thickness of Ni5Zn21 had increased prominently with reaction time. However, there is no observable change in the thickness of NiZn3 and Ni-Zn solid solution during reaction.

    總目錄 中文摘要 I 英文摘要 II 誌謝 IV 總目錄 V 表目錄 VII 圖目錄 VIII 第壹章 緒論 1 1-1 電子構裝技術簡介 1 1-2 電子產品無鉛化之發展 3 1-3 無鉛銲錫合金之種類與性質 3 1-3-1 錫銀（Sn-Ag）系統 6 1-3-2 錫鉍（Sn-Bi）系統 10 1-3-3 錫銦（Sn-In）系統 10 1-3-4 錫鋅（Sn-Zn）系統 13 1-4 金屬基材於液態銲錫中之溶解行為 15 1-5 研究目的 16 第貳章 實驗方法與步驟 19 2-1 實驗構想 19 2-2 實驗材料的準備 19 2-2-1 銲錫的選用 19 2-2-2 金屬基材前處理 19 2-2-3 電鍍鎳層 22 2-3 界面反應的觀察 22 第參章 結果與討論 27 3-1 錫鋅共晶銲錫與電鍍鎳之界面反應行為 27 3-1-1 錫鋅共晶銲錫與電鍍鎳在230℃的反應行為 27 3-1-2 錫鋅共晶銲錫與電鍍鎳在250℃的反應行為 31 3-1-3 錫鋅共晶銲錫與電鍍鎳在270℃的反應行為 36 3-1-4 錫鋅共晶銲錫與電鍍鎳於290℃的反應行為 39 3-1-5 各溫度生成鎳鋅反應層的種類及其厚度與時間之關係 44 3-2 反應層之成長動力學 52 3-2-1 反應機制的探討 52 3-2-2 鎳鋅反應活化能的計算 56 3-2-3 比較本實驗與文獻中鎳與錫鋅銲錫反應 59 3-3 各溫度電鍍鎳層與錫鋅共晶銲錫之界面關係總結 61 第肆章 結論 66 參考文獻 67 表目錄 表1-1 鉛及無鉛銲錫中常添加之金屬的價格 7 表1-2 錫鉛銲錫及常見無鉛銲錫的價格 8 表2-1 電鍍鎳溶液組成及電鍍條件 24 表3-1 在不同反應溫度所生成IMC之種類 49 表3-2電鍍鎳與錫鋅共晶合金於各溫度反應，在各時間區間中反應層的平均成長速率 51 表3-3 鎳與各種無鉛銲錫間介金屬化合物成長所需的活化能 60 表3-4 結晶參數表 65 圖目錄 圖1-1 晶片構裝層級的各種接合方法（a）打線接合，（b）捲帶式自動接合，（c）覆晶接合 2 圖1-2 一般IC元件在晶片構裝與基板構裝之流程 4 圖1-3 錫鉛二元相圖 5 圖1-4 錫銀二元相圖 9 圖1-5 錫鉍二元相圖 11 圖1-6 錫銦二元相圖 12 圖1-7 錫鋅二元相圖 14 圖1-8 銲錫隆點之基本結構 18 圖2-1 實驗流程圖 20 圖2-2 金屬基材前處理過程 21 圖2-3 電鍍鎳裝置示意圖 25 圖2-4 浸鍍實驗配置圖 26 圖3-1 電鍍鎳與錫鋅共晶銲錫於250℃反應120分鐘浸鍍界面處之形態 28 圖3-2 電鍍鎳與錫鋅共晶銲錫於230℃反應不同時間之界面形態（a）10分鐘，（b）20分鐘，（c）40分鐘，（d）60分鐘，（e）90分鐘，（f）120分鐘 29 圖3-3 鎳鋅二元相圖 30 圖3-4 電鍍鎳與錫鋅共晶銲錫於230℃反應，Ni5Zn21 IMC厚度與時間的關係圖 32 圖3-5 電鍍鎳與錫鋅共晶銲錫於250℃反應不同時間之界面形態（a）10分鐘，（b）20分鐘，（c）40分鐘，（d）60分鐘，（e）90分鐘，（f）120分鐘 33 圖3-6 電鍍鎳與錫鋅共晶銲錫於250℃反應，Ni5Zn21 IMC厚度與時間的關係圖 34 圖3-7 電鍍鎳與錫鋅共晶銲錫於250℃下反應不同時間之界面離子影像及EDS成份分析結果（a）40分鐘，（b）60分鐘，（c）90分鐘，（d）120分鐘。 35 圖3-8 電鍍鎳與錫鋅共晶銲錫於250℃反應，離子影像中觀察到各層的厚度及反應層總厚度與時間的關係 37 圖3-9 電鍍鎳與錫鋅共晶銲錫於270℃反應不同時間之界面形態（a）10分鐘，（b）20分鐘，（c）40分鐘，（d）60分鐘，（e）90分鐘，（f）120分鐘 38 圖3-10 電鍍鎳與錫鋅共晶銲錫於270℃反應，各IMC層厚度與時間的關係圖 40 圖3-11 電鍍鎳與錫鋅共晶銲錫於270℃下反應不同時間之界面離子影像及EDS成份分析結果（a）40分鐘，（b）60分鐘，（c）90分鐘，（d）120分鐘 41 圖3-12 電鍍鎳與錫鋅共晶銲錫於270℃反應，離子影像中觀察到各層的厚度及反應層總厚度與時間的關係 42 圖3-13 電鍍鎳與錫鋅共晶銲錫於290℃反應不同時間之界面形態（a）10分鐘，（b）20分鐘，（c）40分鐘，（d）60分鐘，（e）90分鐘，（f）120分鐘。 43 圖3-14 電鍍鎳與錫鋅共晶銲錫於290℃反應，生成Ni5Zn21 IMC厚度與時間的關係圖 45 圖3-15 電鍍鎳與錫鋅共晶銲錫於290℃下反應不同時間之界面離子影像及EDS成份分析結果（a）40分鐘，（b）60分鐘，（c）90分鐘，（d）120分鐘 46 圖3-16 電鍍鎳與錫鋅共晶銲錫於290℃反應，離子影像中觀察到各層的厚度及反應層總厚度與時間的關係 47 圖3-17 電鍍鎳與錫鋅共晶合金於各溫度反應，反應層總厚度與時間關係圖 50 圖3-18 鎳錫二元相圖 53 圖3-19 各反應溫度下，反應層厚度與反應時間之對數圖，（a）230℃，（b）250℃，（c）270℃，（d）290℃ 54 圖3-20 界面IMC層厚度與鋅原子擴散速率的關係，圖中箭號長短代表速率的大小（a）界面反應機制控制，（b）擴散機制控制 57 圖3-21 成長常數與溫度的倒數之關係圖 58 圖3-22 反應界面示意圖（a）250℃，（b）270℃，（c）290℃ 62 圖3-23 在不同反應溫度，電鍍鎳層與錫鋅共晶銲錫之間各反應層的成長 64

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